Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/002—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the linkage of the reactive group being alternatively specified
  • C09B62/006—Azodyes
  • C09B62/012—Metal complex azo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/04—Azo compounds in general
  • C09B45/06—Chromium compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/022—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring the heterocyclic ring being alternatively specified
  • C09B62/026—Azo dyes
  • C09B62/032—Metal complex azo dyes

Definitions

• A is a phenyl or a naphthyl group with no reactive substituents
• B is a phenyl or a naphthyl or a pyrazolyl group with no reactive substituents
• n is at most 3
• A is a sulfonated phenyl or a sulfonated naphthyl group with no reactive substituents and no further ionogenic substituents
• Z is a group containing a substituent which can split oil as :anion
• D can also contain lower alkyl or lower alkoxy, to form the chromium-containing reactive azo dyestufi of the formula
• a -N N-B (SOH) (3 o o Nil-z 110 s y
• the :present invention concerns new chromium containing reactive dyestuffs, processes for the production thereof, their use for the dyeing of cellulose and polyamide material, as well as, as industrial products, the material dyed with the aid of these dyestuffs.
• A represents a radical of the benzene or naphthalene series containing no reactive groups
• B represents a radical of the benzene, naphthalene or pyrazole series containing no reactive groups, each of A and B containing the oxygen O in o-position to the azo bond, and
• A represents a sulphonated radical of the benzene or naphthalene series containing no reactive groups, which radical contains no other ionogenic substituents apart from sulphonic acid groups,
• Z represents a group which contains at least one substituent which can be split off as anion
• the benzene ring D can also contain lower alkyl and alkoxy groups to form a compound of Formula III A N N B I I ($0 K) o o n Cr o o NH z 6) Q H N N A N D? ao s X III wherein A B and n have the meanings given in Formula I, and A Z and D have the meanings given in Formula II.
• a and B represent a radical of the naphthalene series then this is bound either in l-position to the azo group and in 2-position to O or vice versa.
• B is a radical of the pyrazole series then it is the radical of a 1-aryl-, in particular lphenyl-3-methylpyrazole bound in the 4-position to the azo group and in S-position to O.
• A is a radical of the naphthalene series, this can be a 1- as well as a Z-naphthyl radical.
• A is a sulphonated radical of the benzene series containing no reactive groups, which radical contains no other ionogenic substituents apart from sulphonic acid groups.
• the aromatic rings of B and A can contain the substituents usual in azo dyestuffs as defined, for example lower alkyl groups such as the methyl or ethyl group, lower alkoxy groups such as the methoxy or ethoxy group, halogens such as chlorine or bromine, sulphonic acid amide groups, lower alkylsulphonyl groups or the nitro group.
• the aromatic ring of A preferably contains a sulphonic acid group and/or a nitro group.
• the reactive group Z contains mainly mobile halogen atoms, preferably chlorine, but also bromine; or also sulphonic acid groups.
• the mobility of these atoms is due to the presence of tertiary ring nitrogen atoms in heterocycles of aromatic character, preferably G-membered heterocycles having at least two tertiary ring nitrogen atoms.
• Z is the radical of a cyclic imide halide of carbonic acid, in particular a triazinyl radical containing at least one mobile halogen atom, e.g. a chloroor bromo-s-triazinyl radical which can contain as further substituents halogen, the primary or secondary amino group, an alkoxy, alkylthio, phenoxy or phenylthio group, or an optionally condensed diazinyl radical containing at least one mobile halogen atom which diazinyl radical is bound at a ring carbon atom preferably directly or by way of a CO-linkage, to the NH-group, e.g.
• a dichloro, dibromo, trichloro or tribromo pyrimidyl radical the radical of the 2,4-dichloropyrimidine-5- or 6-carboxylic acid or of the 2,3dichloroquinoxaline-6-carboxylic acid; in particular Z is the trichloro pyrimidyl radical.
• the starting materials of Formulae I and II are known or can be produced by known methods.
• the chromium complexes of Formula I are obtained, for example, by reacting an agent giving off chromium with a monoazo dyestutf of Formula V in an acid medium.
• Azo dyestuffs of Formula II are obtained, for example, by coupling a diazotised aminoazo dyestuff of Formula VI with l-amin-8-hydroxy-3,6- or -4,6-disulphonic acid in an alkaline medium to form the aminodisazo dyestutf of Formula VII on ⁇ II no Nli so a ' VII and reacting the latter with an acylating agent introducing the radical Z.
• the halides of the carboxylic acids mencases; generally however, it is necessary to evaporate the aqueous solution to dryness in order to isolate the end product.
• the starting material of Formula IV is obtained, for example, by reacting a complex chromium compound of Formula I with an aminodisazo dyestutf of Formula VII under the conditions described for the first process.
• the main acylating agents used to introduce the radical Z are those mentioned in the first process in the description of the production of the starting materials of Formula II.
• the reaction of the amino dyestuff of Formula IV with the agent introducing the radical Z is performed in the usual manner, advantageously in aqueous medium, if desired in the presence of inert organic solvents which can easily be removed such as low aliphatic ketones, e.g. acetone, and it is preferably performed in the presence of mineral acid buffering agents such as sodium or potassium carbonate, sodium or potassium hydroxide solution, dior trisodium phosphate or dior tri-potassium phosphate, sodium or potassium acetate or tertiary nitrogen bases such as pyridine.
• mineral acid buffering agents such as sodium or potassium carbonate, sodium or potassium hydroxide solution, dior trisodium phosphate or dior tri-potassium phosphate, sodium or potassium acetate or tertiary nitrogen bases such as pyridine.
• the new chromium containing 2:1 complexes of Formula III are dark powders. In the form of their alkali metal salts they dissolve well in water. They dye cellulose material such as staple fibre, jute, ramie, hemp and, chiefly, cotton, as well as polyamide fibres, e.g. natural polyamide fibres such as wool and silk or synthetic polyamide fibres such as nylon, in brown-black to green-black shades.
• the cellulose material is impregnated or printed, for
• acid binding agents are sodium carbonate, potassium carbonate, diand trisodium phosphate, sodium hydroxide solution and, at temperatures of over 50 C., also potassium or sodium bicarbonate.
• the treatment with these agents can be performed at room temperature or at a raised temperature.
• the acid binding agent can also be added to the impregnating liquors or printing pastes and then the dyeing is developed by short heating at temperatures over 100 C. to C. or by depositing for a longer time at room temperature.
• the new dyestuffs are bound chemically to the fibre by the treatment with acid binding agents.
• the cellulose dyeings have excellent wet fastness properties after soaping.
• Natural polyamide fibres are dyed in a hot, weakly acid, e.g. acetic acid, bath in the presence of auxiliaries which improve the eveness of the dyeing such as fatty acid/alkanolamine polycondensation products as well as, optionally, in the presence of salts such as sodium chlo ride or sulphate.
• Synthetic polyamide fibres are advantageously dyed in a hotacid bath, then rinsed and aftert-reated in a boiling alkaline bath.
• the dyestuffs according to the invention produce very deep dyeings and :are particularly well suited therefore to attain full black shades.
• parts are given as parts by weight.
• the temperatures are in degrees centigrade.
• the relationship of parts by weight to parts by volume is as that of grams to cubic centimetres.
• Example 1 and 88.6 parts of the disazo dyestufi? of the formula are added to 400 parts of 80 hot water.
• the pH of the mixture is adjusted to 6-6.5 by the addition of sodium hydroxide solution While stirring and this pH is maintained until the completion of the reaction.
• the temperature is kept for the whole time at 80-850.
• the newly formed dyestuff is completely dissolved.
• the filtrate is concentrated to dryness in vacuo. A dark powder is obtained which easily dissolves in water.
• 100 parts of wool are introduced at 50 in a dyebath consisting of 4000 parts of water, 6 parts of this dyestuff, 6 parts of 30% acetic acid and 1 part of a condensation product produced by condensing 2 mols of diethanolamine with 1 mol of coconut oil fatty acids, the temperature of the dyebath is then raised within 20 minutes to the boil, and the goods are dyed at the boil for one hour and afterwards rinsed and dried. A deep, blueish black wool dyeing is obtained.
• the starting dyestufi for the above process is obtained Q- if the known chromium complex compound of the formula SOSH N Oz I If cotton is pad dyed with an 8% aqueous solution of the dystuff at 50 in the foulard, which solution contains also 5% of urea and 2% of soduim carbonate, dried at 0 80 and then steamed for 5-10 minutes and soaped at the boil, a deep black dyeing is obtained which is fast 0 Cr to washing.
• H0 8 SO H H03SN l I 10 Same as N o. 9 above. 05 Blueish Cl C 0 Cl black.
• H038 N N Cr N 01f TOCH; -30' Black. 0 0 NH: I 69 N N 01 s oarr 1103s S0 11 Nah I SOaH I claim: adjacent --O in o-position to the azo bond be- 1. A chromium-containing reactive dyestuif of the tween them, the latter being directly connected to formula a ring carbon atom of B,
• n a positive whole number of at most 2
• A represents a monoor 'di-sulfonated radical of the a benzene or naphthalene series which radical con- N N B tains sulfonic acid groups as sole ionogenic sub- 3 stituents, and
• A represents the radical of an azo dyestutf component of the benzene or naphthalene series (containing no reactive groups)
• B represents the radical of an azo dyestutf component of the benzene, naphthalene or l-phenyl-3-met'hyl pyrazole series, each of A and B containing the the preceding formula being selected from the class consisting of lower alkyl and lower alkoxy.
• a chromium-containing reactive dyestufi as defined in claim 1, wherein the radical A -N N is in the pposition to the oxygen --O- and the benzene ring D contains no further substituents.
• a dyestuff he free acid form of which is of the formula l SOsH $1 I NH @"ZZZIQQ Cl Cl SOaH 5.
• a dyestuff the free acid form of which is of the formula 14 6.

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Cited By (7)

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Citations (1)

• 1963
  • 1963-10-07 CH CH1230163A patent/CH430000A/de unknown
• 1964
  • 1964-10-05 US US401639A patent/US3412081A/en not_active Expired - Lifetime
  • 1964-10-06 GB GB40690/64A patent/GB1080056A/en not_active Expired
  • 1964-10-06 BE BE654038D patent/BE654038A/xx unknown
  • 1964-10-06 NL NL6411615A patent/NL6411615A/xx unknown

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